Black substantive sulfur dye and process of making same.



' UNITED STATES PATENT OFFICE.

ALOIDE FRANCOIS POIRRIER, OF PARIS, FRANCE.

BLACK SUBSTANTIVE SULFUR DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 665,547, dated January 8, 1901.

Application filed May 16, 1899. Serial No. 717,039. (No specimens.)

T0 (LZZ whom, it may concern:

Be it known that I, ALOIDE FRANCOIS POIR- RIER, of Paris, France, have invented new and useful Improvements in Black Substantive Sulfurized Dyestuffs,which improvement is fully set forth in the following specification.

I find that new black, substantive dyestuffs of much importance in dyeing cotton are obtainable by melting with sulfur alone or with sulfur and sodium sulfid certain dyestuffs of the indophenol group or of the indoanilin group. These dyestuffs, which form the raw material for the dyestufis manufactured as herein set forth, are made in the known manner by oxidizing a mixture of paraphenylenediamin or paramidophenol on the one hand with phenols ornaphthols on the otherhand. These'easily prepareddyestuffs are then treated in the known manner, as in the following example.

Example: Into fifteen kilos of melted sulfur kept at a temperature of about 130 to 140 centigrade are introduced ten kilos of the dyestufi prepared from paraphenylenediamin andnaphthol, and them'ass is heated for four hours, the temperature being gradually raised to about 200 centigrade. There is thus obtained a friable brittle mass, which is pulverized and introduced in small portions at a time into from sixty to eighty kilos of crystallized sodium sulfid previously fused and evaporated to a syrupy consistency. Equally well after having allowed the mass to cool the sodium sulfid may be added and heated gradually. When once melted the sodium sulfid dissolves little by little the product formed, and there is obtained a pasty mass, which is then heated to about 200 to 250 centigrade. Energetic reaction ensues, and the mass then slowly dries, becoming hard and brittle, in which condition it is suitable for use. In this example, as well as in the claims for the dyestuif mentioned, may be substituted any other dyestuffs belonging to the indophenol group or indo-anilin group, and the proportion of sulfur and sodium sulfid, as well as the temperature and the dura tion of heating, may be varied without sensibly modifying the dyestuffs obtained.

By treating according to the process herein described the coloring-matter resulting from the oxidation of an equimolecular mixture of para-phenylenediaminandalpha-naphthol I obtain a bluish-black powder, which when melted in sulfid of sodium is soluble in water. The solution is of a brownish green color and is precipitated by the acids in the form of blackened yellowish-brown flakes and melts rapidly in the air. Common salt also precipitates the coloring-matter from its solutions. The water solution dyes unmordanted cotton at the boiling-point in the presence of a little common salt. The dyes fixed by oxidation with bichromate of potash are black with blue reflection. In a similar manner by treating according to the process herein described the coloring-matter resulting from the oxidation of an equimolecular mixture of paraphenylenediamin and phenol I obtain a coloringmatter of a very slightly greenish-black appearance, which is very easily soluble in boiling water. The solution thus obtained is of a pretty-dark greenish black. It is precipitated by the acids or by common salt. In the first case the precipitate obtained is of chocolate-brown color and in the air becomes pretty rapidly oxidized into a brownish black. In the second case it is greenish black. The water solution dyes the unmordanted cotton very easily at the boiling-point in the presence of common salt and gives very handsome black colors with purplish reflections after fixation by oxidation with bichromate of potash.

In referring in this specification to the indophenolic groupsl have followed the classification adopted by Behel and other authors, who also apply that term to a specific class coming under the general group termed indophenolic. To-make the description and claims entirely clear, it may be stated that the coloring-matters treated according to this invention belong to a general class represented by the formula These form no part of the present or when both are OH groups, the derived colorin g-m atters are those which are treated according to this invention and which are designated by Julius by the generic terms indo-anilin anc indophenolic, distinguishing them from the indamins above referred to. These two species are equivalent for the purposes of the present invention.

In the following claims the term indophenolic is employed with its generic meaning.

I claiIn 1. The process of manufacturing black substantive coloring-matters which process consists in heating the herein-described coloringmatters of the indophenolic group with sulfur.

2. The process of manufacturing black sub stantive coloring-matters which process consists first in heating the herein-described 001- 

